Deuterated semiconducting organic compounds used for opto-electronic devices

ABSTRACT

Organic semiconductors consisting of conjugated chromophores wherein one or more hydrogen atoms are deuterated are disclosed. Methods of preparing such organic semiconductors are described. The organic semiconducting compounds exhibit remarkably high luminescence and good thermal stability. Applications of these materials for optoelectronic devices, such as light-emitting devices and photodiodes, with enhanced performance and lifetime are disclosed. The disclosed materials can be used as emissive layer, charge-transporting layer, or energy transfer (i.e. phosphorescence dopant) material in organic light-emitting devices.

TECHNICAL FIELD

[0001] The present invention relates to new semiconducting organiccompounds and/or polymers for use in optoelectronic devices that containcompletely or partially deuterated conjugated backbones, which canpromote luminescence and thermal stability of the materials. Moreparticularly, the present invention relates to the effectivemodification of the molecular structure of known luminescent materialswith conjugated backbones containing hydrogen atoms by replacing one ormore of the hydrogen atoms with deuterium atoms. The resultingdeuterated material is significantly altered and has greatly improvedperformance over known luminescent light-emitting materials.

BACKGROUND OF THE INVENTION

[0002] Organic semiconductors have the benefit of low cost processing,easy control of properties by changing chemical structures, andattractive electronic properties. These materials are usually composedof conjugated chromophores linked by saturated or unsaturated linkageunits. Many interesting applications have been explored in recent years,such as organic light-emitting devices [C. W. Tang, S. A. Van Slyke,Appl. Phys. Lett., 1987, 51(12), 913; J. H. Burroughes; D. D. C.Bradley; A. R. Brown; R. N. Marks; K. Mackay; R. H. Friend; P. L. Bumand A. B. Holmes, Nature 1990, 347, 539. R. H. Friend; R. W. Gymer; A.B. Holmes; J. H. Burroughes; R. N. Marks; C. Taliani; D. D. C. Bradley;D. A. Dossantos; J. L. Bredas; M. Logdlund and W. R. Salaneck, Nature1999, 397, 121.], organic lasers [F. Hide; M. A. Diaz-Garcia; B. J.Schwartz and A. J. Heeger, Acc. Chem. Res. 1997, 30, 430.], organicthin-film transistors [F. Gamier, R. Hajlaoui, A. Yassar, P. Srivastava,Science, 1994, 265, 1684], and organic photodiodes.

[0003] One application of organic semiconductors is as an activeflat-panel display or organic light-emitting device (OLED). Such devicesoffer many unique features, including a low cost, full color, activedisplay with the possibility of a thinner, lighter, larger and moreflexible display module, with wider viewing angles (>160°), compared toconventional flat-panel display devices. All these features imply astrong competitive alternative to replace present LCD displays. Suchdevices consist of one or several semiconducting organic layer(s)sandwiched between two electrodes. When an electric field is applied,electrons are injected by the cathode into the lowest un-occupiedmolecular orbital (LUMO) of the adjacent molecules, and holes areinjected by the anode into the highest occupied molecular orbital(HOMO). As a result of recombination of electrons and holes, an excitedstate, called singlet exciton, is formed which returns back to theground state upon emission of light corresponding to the energy band gapof the emissive material. The selection of emissive materials not onlycan influence the emission color, but also the light emission efficiency(photons per injected electron) and the light emission brightness andlifetime. In practical display applications, color purity,light-emission efficiency, brightness and lifetime are importantparameters.

[0004] There have been various organic semiconductor materials developedin the past a few years [Y. Sato, Semiconductors & Semimetals, 2000, 64,209; A. Kraft; A. C. Grimsdale and A. B. Holmes, Angew. Chem.—Int. Ed.In Engl. 1998, 37, 402; Li, X. -C., Moratti, S. C.; In Photonic PolymerSystems: Fundamentals, Methods, and Applications; Wise, D. L.; Wnek, G.E.; Trantolo, D. J.; Cooper, T. M.; Gresser, J. D.; Eds.; Marcel Dekker,Inc.: New York, Chapter 10, 1998, p. 335]. Many prototypes of OLEDdisplay modules have been demonstrated with the use of organicluminescent compounds (small molecular compounds or polymers). However,only limited commercial products of OLEDs have been launched, due bothto the difficulty of technological integration and to the overallperformance of the present organic semiconducting materials, whichinclude emissive materials and charge transporting materials.Accordingly, there is a need in the art to develop new materials thatexhibit combinatory high performance of luminescence, excellentstability, and good lifetime.

[0005] The search for new organic materials used for optoelectronicdevices, such as organic light-emitting devices, has been a very activefield in recent years. This includes research relating to organicsemiconductors and organic polymeric materials that present strongluminescence and good processibility. Most researchers have focused onvarying the structure of either the core chromophore and/or polymerbackbone, and on modifying linkages for solubility, for charge injectionability, or for other processing functionality. These methods requireinnovative molecular design, coupled with skillful chemical synthesis,which are time consuming and expensive in order to screen off undesiredproducts.

[0006] It is an object of the present invention to provide a unique andeffective manner to chemically modify known and novel optoelectronicmaterials by replacing protons with deuterium atoms on the conjugatedchromophores. It is another object of the invention to provide a methodto design and synthesize new luminescent organic materials containingdeuterium atoms for their application in optoelectronic devices, such aslight-emitting devices. It is further another object of the invention toimprove OLED performance with brighter luminance and better thermalstability.

SUMMARY OF THE INVENTION

[0007] The present invention relates to deuterated semiconductor organiccompounds used in optoelectronic devices and to processes of preparingsuch deuterated compounds. In one process within the scope of thepresent invention, known and novel organic semiconductor compounds aredeuterated by replacing one or more hydrogen atoms covalently bonded tocarbon atoms with deuterium atoms.

[0008] Deuterium is a non-radiative isotope of hydrogen, which issometimes called heavy hydrogen due to its doubled atomic mass. Thedifference between hydrogen and deuterium has fairly small chemicaleffects; however, there are important physical effects because of themass difference between the isotopes. The heavier isotope, deuterium,lies lower in the potential well, and hence has a lower zero-pointenergy and vibration frequency, and smaller vibration amplitude thanhydrogen. Because of the asymmetry of the potential well, bond lengthsand bond angles involving deuterium are different than those involvinghydrogen. The observed smaller amplitude of the C-D stretching andbending motion, relative to C-H, should be best accounted for with asmaller van der Waals radius for D than for H. The weak vibroniccoupling in the deuterated system has been used to theoretically predicthigher fluorescence quantum yield [A. L. Burin and M. A. Ratner, J.Chem. Phys., 1998, 109, 6092]. Spectroscopic studies indicate thatdeuterated phenanthrene has a smaller non-radiative triplet rateconstant than its aromatic molecule [S. M. Ramasamy, R. J. Hurtubise,Appl. Spectroscopy, 1996, 50(9), 1140].

[0009] Deuterium is also found to act as an apparent electron-donatinginductive substituent relative to hydrogen. The isotope effects may beapplied in the design of new luminescent materials with enhancedcharge-injection ability. Additionally, it is know that the C-D bond isshorter than the C-H as a result of the anharmonicity of the bondstretching potential. [M. L. Allinger and H. L. Flanagan, J.Computational Chem. 1983, 4(3), 399]. This means the carbon-deuteriumchemical bond is stronger, more stable, and reacts more slowly than thecarbon-hydrogen chemical bond, so that the deuterated organic system hasbetter thermal stability, and longer lifetime in optoelectronic devices.Deuterated luminescent material may also have a higherelectroluminescent quantum yield as a result of smaller non-radiativetriplet rate.

[0010] In the prior art, deuterated hydrocarbon lubricants have betteranti-oxidation and improved stability than normal hydrocarbon lubricants[U.S. Pat. No. 4,134,843]. A deuterated polymer has been used foroptical fiber with low attenuation optical loss [U.S. Pat. No.RE031,868]. Deuterated pharmaceuticals or drugs can enhance drug'sefficacy and activity. [U.S. Pat. No. 4,898,855 and U.S. Pat. No.5,846,514]. Deuterium-treated semiconductor devices have been disclosed[U.S. Pat. No. 5,872,387], wherein degradation of inorganicsemiconductor devices has been reduced by using deuterium passivation;deuterium incorporation at the SiO₂/Si interface has been reported toimprove the hot carrier reliability of CMOS transistors. [J. Lee, K.Cheng, et al, IEEE Electron Device Letters, 2000, 21(5), 221]. Comparedwith normal hydrogen treated device, the deuterium treated device has asignificant lifetime improvement (90 times).

[0011] The deuterated organic semiconductor materials within the scopeof the present invention are preferably luminescent. Luminescence heremeans either fluorescence (singlet emission) or phosphorescence (tripletemission). The deuterated organic semiconductor materials may possesscharge injection (electron injection or hole injection), hole blocking,or exciton blocking properties. As used herein, hole blocking propertymeans that the semiconductor material allows electrons to transport, butnot holes. Whenever a material has a low mobility for hole transporting(less than 10⁻⁶ cm/V·s), or a very high HOMO (highest occupied molecularorbital) level, the material normally possesses hole blockingproperties. As used herein, exciton blocking property means thatexcitons are confined within an emissive layer by using another materiallayer which does not readily transport excitons (usually non-emissivelayer).

[0012] The deuterated organic semiconducting material preferablypossesses a strong energy transfer property. As used herein, energytransfer includes a Forster process where a higher energy singlettransfers to a lower energy singlet. An example is a blue emissivepolymer (host) doped with red emissive material (guest) [liketetraphenylporphyrin doped polyfluorene reported by T. Virgili, et al.,Adv. Mater., 2000, 12(1), 58]. The doping level is usually from 0.1-15%,but more than 90% energy will transfer into the red emissive material,thus lead to red emission rather than blue emission. As used herein,energy transfer also includes an intersystem transfer where the singletenergy transfers to a triplet, and thus lead to phosphorescence. Anexample is a yellow emissive polymer doped with rare earth metalcomplexes to lead to electrophosphorescence [M. D. McGehee, et al., Adv.Mater., 1999, 11(16), 1349; Appl. Phys. Lett., 1999, 75, 4]. Thistriplet-emission can potentially lead to very high quantum efficiencybecause the maximal probability of a triplet is 75%.

[0013] The deuterated organic semiconducting materials preferablyproduce more singlet energy states for light-emission, compared tonon-deuterated materials. For most organic fluorescent materials, themaximum singlet production probability under electrical excitation isabout 25%. Deuterated materials may exceed that limit forelectrofluorescence because of their slow triplet production rate.Therefore, deuterated materials may efficiently produce more singletsthan non-deuterated materials, with a potential singlet productionexceeding 25%.

BRIEF DESCRIPTION OF THE DRAWINGS

[0014]FIG. 1 is a cross-section illustration of a typical single layerlight emitting device.

[0015]FIG. 2 is a cross-section illustration of a typical triple layerlight emitting device.

[0016]FIG. 3 is a graph of the UV spectrum of the sulfonium polymerprecursor and the converted conjugated polymer deuterated PPV (D-PPV),showing the band gap changes from 3.42 eV to 2.45 eV.

[0017]FIG. 4 is a graph of the ultraviolet (UV) and visiblephotoluminescent spectrum of the deuterated polymer D-PPV.

[0018]FIG. 5 is a graph of the ultraviolet (UV) spectra and thephotoluminescent spectrum (excited by 400 nm UV light) ofsemi-deuterated MEH-PPV.

[0019]FIG. 6 is a graph of the electroluminescence spectrum of Ir(ppy)₃in the device structure of ITO/NPD 40 nm/CBP+11% Ir(ppy)₃ 20 nm/BCP 10nm/Alq3 40 nm/LiF 0.75 nm/Al.

[0020]FIG. 7 is a graph of the electroluminescent spectrum ofIr(ppy)₃-d8 in the device structure of ITO/NPD 40 nm/CBP+11% Ir(ppy)₃-d820 nm/BCP 10 nm/Alq3 40 nm/LiF 0.75 nm/Al.

[0021]FIG. 8 is a comparison graph of the relationship of externalquantum efficiency vs. current density for the device in Example 10(square) and for the device in Example 11 (circle).

[0022]FIG. 9 is a comparison graph of the relationship of luminanceefficiency vs. current density for the device in Example 10 (square) andfor the device in Example 11 (circle).

DETAILED DESCRIPTION OF THE INVENTION

[0023] Virtually all organic luminescent materials now marketed containhydrogen atoms, each of which has a molecular mass of one. According tothe present invention one or more of the hydrogen atoms on a conjugatedchromophore or a conjugated polymer are deuterated. The molecular massbecomes higher, and the optical and electronic properties of theconjugated luminescent material are altered and improved. The deuteratedorganic semiconductor has improved performance, for instance, higherfluorescence yield and more stability than its non-deuterated analogue.

[0024] There are several deuterated structures or structuralcombinations that may be used to form conjugated chromophores that areuseful for opto-electronic applications, with particularly applicationin light-emitting devices.

[0025] 1. A conjugated chromophore, as used herein, includes a linearconjugated organic compound or a polymer with at least 5 conjugatedbonds, wherein protons linked to the conjugated bonds are partially orfully deuterated. Examples of typical backbones of conjugatedchromophore compounds for this category can be described as in Scheme 1:

[0026] If partially deuterated, the un-deuterated sites for thecompounds or polymers in Scheme 1 may be linked with hydrogen atoms,halogens such as F, Cl, Br, etc; or alkyl, alkoxyl, thiol, silyl;aromatic rings such as phenyl and naphthalene; or heteroaromatic rings,such as thiophene, pyridine, and quinoline.

[0027] 2. A conjugated chromophore, as used herein, also includes acyclic ring, fused cyclic ring, and combinations thereof, that form aconjugated organic compound or a polymer with at least 5 conjugatedbonds, wherein protons linked to the conjugated bonds are partially orfully deuterated. Examples of typical backbones of conjugated organiccompounds for this category can be described as in Scheme 2, below. Theprotons linked with aromatic rings of the compounds in Scheme 2 shouldbe partially or fully deuterated. If partially deuterated, theun-deuterated sites may be linked with hydrogen atoms, halogens such asF, Cl, Br, etc.; or alkyl, alkoxyl, thiol, silyl; aromatic rings such asphenyl and naphthalene; or heteroaromatic rings, such as thiophene,pyridine, and quinoline.

[0028] 3. A conjugated chromophore, as used herein, also includesheterocyclic ring, fused heterocyclic ring, and combinations thereof,that form a conjugated organic compound or a polymer with at least 5conjugated bonds, wherein protons linked to the conjugated bonds arepartially or fully deuterated. Examples of typical backbones ofconjugated organic compounds for this category can be described as inScheme 3. The protons linked with the heterocyclic rings of thecompounds in Scheme 3 should be partially or fully deuterated. Ifpartially deuterated, the un-deuterated sites may be linked withhydrogen atoms; halogens such as F, Cl, Br, etc.; alkyl, alkoxyl, thiol,silyl; aromatic rings such as phenyl and naphthalene; or heteroaromaticrings, such as thiophene, pyridine, and quinoline.

[0029] 4. A conjugated chromophore, as used herein, also includes ametal chelated compound or a organometallic compound with a formula ofCAMB, where C denotes a chromophore selected from category 1, 2 or 3;and M denotes a metal selected from, Li, Na, K, Be, Mg, Ca, Ti, Cr, Mo,Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, Cd, B, Al, Ga, In, Si,N, P; A and B denote the number from 1 to 10, preferentially 1-4. Theprotons linked with the chromophore material of the compounds in Scheme4 should be partially or fully deuterated. Examples of this categorycompounds are presented in Scheme 4. If partially deuterated, theun-deuterated sites may be linked with hydrogen atoms, halogens such asF, Cl, Br, etc.; alkyl, alkoxyl, thiol, silyl; aromatic rings such asphenyl and naphthalene; or heteroaromatic rings, such as thiophene,pyridine, and quinoline.

[0030] 5. A conjugated chromophore, as used herein, also includes acombination of the compounds disclosed in categories 1, 2, 3 and 4,above, to form a conjugated organic compound or a polymer with at least5 conjugated bonds wherein protons linked to the conjugated bonds arepartially or fully deuterated. A few examples of compounds within thiscategory compounds are presented in Scheme 5. If partially deuterated,the un-deuterated sites may be linked with hydrogen atoms, halogens suchas F, Cl, Br, etc.; alkyl, alkoxyl, thiol, silyl; aromatic rings such asphenyl and naphthalene; or heteroaromatic rings, such as thiophene,pyridine, and quinoline.

[0031] The present invention is also directed to organic electronicdevices containing the foregoing deuterated conjugated semiconductingcompounds and polymers. Such devices typically include at least one thinfilm of the deuterated conjugated compound or polymer coupled to a pairof electrodes. Additional thin films of conjugated semiconductingmaterial can be used. In such cases, one thin film may be configured topromote electron transport and a second thin film may be tuned topromote hole transport. When the organic electronic device is fabricatedwith a plurality of thin films of conjugated semiconducting compounds orpolymers, the thin films are preferably tuned to promote balancedelectron and hole transport between the first and second electrodes.Typical organic electronic devices include, but are not limited to, aLED, a thin film transistor, a photovoltaic solar cell, anelectrochemical luminescent display device, an electrochromic displaydevice, and an electroluminescent device for active flat-panel displayapplications.

[0032]FIG. 1 shows the sectional structure of a typical single layerlight-emitting device 10. The LED device 10 includes a clear substrate12 having an anode coating 14. A single layer of deuteratedsemiconducting luminescent polymer 16 is deposited between the anode 14and a cathode 18. An electrical potential 20 connects the anode 14 andcathode 18.

[0033] In many cases, a double or a multi-layer LED may be fabricated,in which one or two different charge-transporting layers are used. Thecharge-transporting layer may be an electron-transporting layer or ahole-transporting layer. Each individual layer may be a polymeric ororganic film with a thickness less than 1500 μm, preferably less than300 nm.

[0034]FIG. 2 shows a section diagram of a typical three-layer LED 30. Asshown in FIG. 2, the anode substrate 34, preferably ITO on a clearsubstrate 32, may be pre-coated with a layer of a hole-transportingmaterial 36 either by spin-coating, or by printing. A typicalhole-transporting layer 36 can be selected from, but not limited to,polyaniline, poly(phenylenevinylene), poly(3,4-ethylenedioxy-thiophene)(PEDOT) (doped with polystyrene sulfonic acid), poly(N-vinyl carbazole)(PVK), or an aromatic amine organic compound or polymer. The thicknessof the hole-transporting layer 36 is preferably between 0.5 nm to 500nm, and more preferably less than 150 nm. A deuterated semiconductingluminescent polymer layer 38 is disposed on the hole-transportingmaterial 36. The solvent used to fabricate the luminescent polymer layer38 is selected to be compatible hole-transporting layer 36 such that itdoes not dissolve the hole-transporting layer 36. Depending on theluminescent polymer utilized, the luminescent layer 38 can emit variouscolors from red, yellow, green, to blue. The thickness of theluminescent layer 38 is preferably between 10 nm to 300 nm, preferablybetween 50 nm to 200 nm.

[0035] The device 30 may be further coated with a layer of anelectron-transporting material 40 either by spin-coating or by printing.A typical electron-transporting layer 46 can be selected from, but isnot limited to, poly(aromatic oxadiazole) [X. -C. Li, et al., J. Chem.Soc. Chem. Commun., p. 2211, 1995], organic compounds containingaromatic oxadiazoles, triazoles, quinolines, such as2-tert-butyl-phenyl-5-biphenyl-1,3,4-oxadiazole (PBD), and Alq3.Evaporation or solution coating may be employed. For solution coating(spin-coating or printing), it is again important to select a suitablesolvent for the electron transporting solution or ink that does notcorrode or dissolve the luminescent polymer layer 38, hole-transportinglayer 44, or anode 42. Luminescent polymers formulated as luminescentink with cross-linking ability may be used. In a preferred embodiment,the cross-linking process can be accomplished by UV irradiation ormoderate thermal treatment (less than 300° C.) of the inked anodesubstrate after printing.

[0036] The cathode metal 42 can be deposited either by thermal vacuumevaporation, or by sputtering. The presently preferred cathode metalsare aluminum, calcium and magnesium. The thickness of the cathode layer42 is preferably between 0.5 nm to 5000 nm, preferably thicker than 50nm. An electrical potential 44 connects the anode 34 and cathode 42.

EXAMPLES

[0037] The following examples are given to illustrate variousembodiments within the scope of the present invention. These are givenby way of example only, and it is to be understood that the followingexamples are not comprehensive or exhaustive of the many types ofembodiments of the present invention that can be prepared in accordancewith the present invention.

Example 1 Green Luminescent poly(phenylene vinylene) with Deuterium viaBromo-Precursor Route

[0038]

[0039] Synthesis of Deuterated 1,4-bisbromomethyl-benzene 2

[0040] Deuterated Xylene-d10 (1.644 g, 14.14 mmol) andN-bromosuccinimide (NBS) (5.6 g, 28.99 mmol) were dissolved in carbontetrachloride (15 mL) at room temperature. After being degassed 3 times,the mixture was heated by an IR lamp to reflux using light irradiation.The reaction was carried out for 6 hours, and cooled down to roomtemperature. After filtration, the solid was washed by dichloromethane(3×30 mL), and the solution portions were collected. Evaporation of thesolvents gave oil product that was purified by silica flash column usinghexane and the mixture of ethyl acetate/hexane (1:10, v/v) to give whitesolid 2 (1.87 g, 49%). Rf=0.46 (EtOA/hexane, 1:3, v/v).

[0041] Synthesis of Bromo-Precursor Deuterated PPV 3

[0042] Deuterated 1,4-bisbromomethyl-benzene 2 (0.8 g, 2.941 mmol) wasdissolved in anhydrous tetrahydrofuran (7 mL) and degassed. The solutionwas cooled down to 0° C. using an ice bath. Potassium tert-butoxide(2.94 mL, 1.0 M in THF, 2.94 mmol) was added into the solution dropwise.The addition was finished within 20 minutes, and the light yellowsolution was stirred at 0° C. for 4 hours. The solution was poured intomethanol (100 mL) to give the precursor polymer precipitate (58%).

[0043] Luminescent Thin Film of Deuterated PPV 4 via Bromo-Precursor 3

[0044] The yellow polymer 3 can be soluble in THF, and a thin polymerfilm of 3 can be cast on a glass substrate. Green luminescent polymer 4can be obtained by heat treatment of 3 at 160° C. for 4 hours undernitrogen or under vacuum.

Examples 2 Green Luminescent Poly(phenylene vinylene) with DeuteriumSubstituents via Sulfonium-Precursor Route

[0045]

[0046] Synthesis of Sulfonium Monomer 5

[0047] Deuterated 1,4-bisbromomethyl-benzene 2 (1.0 g, 3.676 mmol) andtetrahydrothiophene (1.62 g, 18.5 mmol) were dissolved in anhydrousmethanol (12 mL), and the mixture was heated to 50° C. The reaction wascarried out under nitrogen for 16 hours. The solvent was evaporatedunder vacuum to give white slurry that was washed by anhydrouschloroform (1×8 mL). The beige powder was dried under vacuum at 0° C. toyield the sulfonium monomer 5 (1.2 g, 68%).

[0048] Synthesis of Sulfonium-Precursor Deuterated PPV 6

[0049] The sulfonium monomer 5 (1.1 g, 2.30 mmol) was dissolved inmethanol (8 mL) at 0° C. The mixture was degassed before the addition ofsodium hydroxide (5.6 mL, 0.4 N in water, 2.25 mmol). The addition ofNaOH was finished within 15 min. After reaction at 0° C. for 2 hours,the colorless solution was dialyzed against degassed water using adialysis tube (Lancaster) to remove oligomers and inorganic species. Thedialysis process was repeated for 2 more times, with final dialysisagainst methanol. The resulting polymer 6 has a yield of 60%, and it isready to prepare polymer thin films.

[0050] Luminescent Thin Film of Deuterated PPV 7 via Sulfonium-Precursor6

[0051] The sulfonium polymer 6 is soluble in water and methanol, and isstable at 0° C. Polymer 6 is normally obtained in the mixture solvent ofmethanol and water with a concentration of 1% which is ready to castthin film on glass substrate. Green luminescent polymer 7 can beobtained by heat treatment of 6 at 160° C. for 4 hours under nitrogen orunder vacuum.

[0052] When the polymer 6 is converted to 7, its conjugation length isincreased which is shown in the UV-Visible spectroscopy. FIG. 3 showsthe UV spectral change of this conversion, showing the band gap changesfrom 3.42 eV to 2.45 eV. After conversion, the polymer 7 fluorescesgreen with the PL peak located at 550 nm, shown in FIG. 4.

Example 3 Normal PPV Polymer Synthesis via Sulfonium Srecursor (forcomparison)

[0053] Normal PPV precursor polymer can be obtained by polymerization ofthe monomer, (Aldrich) following the similar procedure as illustrated inexample 2. The normal PPV polymer has very similar optical andelectronic properties as D-PPV. Comparative photoluminescence (PL)quantum efficiency measurements showed that the deuterated PPVphotoluminescence quantum efficiency compared to that of normal PPV was:DPPV/PPV=1.2, which means that the deuterated PPV has a brighterphotoluminescence than normal PPV.

Example 4 Red Luminescent Partially Deuteratedpoly(2-methoxy-5-ethylhexyloxy-phenylene Vinylene) (Partially DeuteratedMEH-PPV)

[0054]

[0055] The Synthesis of 1-(2-ethyl-hexyloxy)-4-methoxy-benzene 9:

[0056] 4-methoxylphenol (24.8 g, 200 mmol) and sodium hydroxide pellets(8.8 g, 220.0 mmol) were charged into a 500 mL two neck flask equippedwith a condenser and a septum. The flask was degassed 3 times beforeadding anhydrous methanol (150 mL) via an annular tube. The solutionbecame hot while stirring. It was heated to reflux for 20 min, and thencooled down to room temperature. 2-Ethyl-hexyl bromide (39 mL, 220 mmol)was then added by a syringe at room temperature, dropwise (15 min.). Themixture was heated to reflux for 20 hour. The methanol was removed bydistillation, and then 150 mL ether was added. Deionized water (100 mL)was added to dissolve inorganic salts. The aqueous phase was washed byether (3×50 mL), and the combined portions of ether was washed by brine(2×50 mL), dried over sodium sulfate, and evaporated to remove ether.The obtained oil was fraction distillated to remove the unreactedethylhexyl bromide, and the final product was collected in the fractionof 130-135° C. (2 mm Hg) as a clear oil (35.8 g, 76%).

[0057] Synthesis of1,4-bis-chloromethyl-d4-2-(2-ethylhexyloxy)-5-methoxy-benzene 10

[0058] 1-(2-ethyl-hexyloxy)-4-methoxy-benzene 9 (5.9 g, 24.97 mmol) andparafoadehyde-d2 were charged into a 100 mL two neck flask, and degassedby pumping/nitrogen inlet (3 times). Hydrochloric acid (37%, 11.2 mL,500 mmol) was added by a syringe. While stirring at room temperature,acetic anhydrate was added dropwise to control keep the reaction mixturefrom becoming too hot. The addition of the acetic anhydrate was finishedwithin 30 minutes. The mixture was then heated to 75° C. under nitrogenwhile stirring. After reaction of 8 hours, the mixture was poured intowater (200 mL), and the aqueous phase was extracted with ethyl acetate(3×80 mL). The combined organic phase was washed with brine (2×50 mL),dried over magnesium sulfate. Evaporation of the organic solvent yieldedthe crude slurry, which was purified by a silica flash column usinghexane and ethyl acetate/hexane mixture (10% to 20%) to give the product(45%). Rf=0.66 (EtOAC/hexane, 1/3, v/v).

[0059] Synthesis of Poly(2-methoxy-5-ethylhexyloxy-phenylene Vinylene)with Deuterium Substituent on Vinyl (Partially Deuterated MEH-PPV) 11

[0060] 1,4-bis-chloromethyl-d4-2-(2-ethylhexyloxy)-5-methoxy-benzene 10(0.62 g, 1.84 mmol) was charged into a 100 mL two neck flask anddegassed by pumping/nitrogen inlet (3 times). Anhydrous tetrahydrofuran(60 mL) was added to dissolve the monomer. Potassium tert-butoxidesolution (11.0 mL, 1.0 M in THF, 11.0 mmol) was added dropwise into thestirring solution within 20 min. The colorless solution became red andviscous. The reaction was carried out under nitrogen for 18 hours underdark condition. The viscous solution was poured into methanol (300 mL)to give a red precipitate, which was purified by repeated precipitation(2 times more) from its solution of chloroform into methanol. A redpolymer was obtained with a yield of 56%.

[0061] The partially deuterated MEH-PPV had a π-π* band gap of 2.1 eV asillustrated in FIG. 5. The polymer luminesces red in solution and inthin film states. FIG. 5 shows the photoluminescent spectrum (excited by400 nm UV light), showing a red luminescent color (located around 620nm).

Example 5 Red Luminescent MEH-PPV with Deuterium Atom Substituents onBoth Vinyl and on Phenyl

[0062]

[0063] According to the above synthesis scheme, the red luminescentdeuterated MEH-PPV 15 is prepared following the similar chemicalprocedure as described in Example 4. The compound 13 is prepared by thechemistry procedure described in: H. Tsuzuki, et al., J. Chem. Research,1994, 1701-1716.

Example 6 Red Luminescent Poly(2,5-dioctyl-phendylene Vinylene) withDeuterium Atom Substituents on Vinyl and on Phenyl

[0064]

[0065] By using the deuterated starting compound 16, red luminescentpoly(dioctylocyl-phenylene vinylene) 19 can be prepared according to theabove scheme with the similar procedures as described in Example 4.

Example 7 Blue Luminescent poly(9,9′-dioctyl-fluorene) with Deuteriumatom Dubstituents

[0066]

[0067] By using the deuterated fluorene 20, blue luminescentpoly(9,9-dialkyl fluorene) 23 can be prepared according to the abovescheme with the similar procedures as described in E. P. Woo et al.,U.S. Pat. No. 5,962,631.

Example 8 Phosphorescent Dopant Metal Complex with Deuterium Atoms

[0068]

[0069] By using the deuterated compound 24, phosphorescent dopant metalcomplex 28, fac-tris(2-phenylpyridine)iridium (Ir(ppy)3), was preparedaccording to the above scheme with the similar procedures andapplication mechanism as described in [M. D. McGehee, et al., Adv.Mater. 1999, 11(16), 1349; Appl. Phys. Lett., 1999, 75, 4].

[0070] D-9-2-Phenylpyridine 26 was synthesized according to OrganicSyntheses Vol. 2, p. 517. The yield of the compound was 21%.D-24-Ir(ppy)3 28 was synthesized according to Inorganic Chemistry, 1991,30(8), 1685. The yield of this compound was 19%. These compounds wereconfirmed by 1H-NMR, which showed no signals due to protons. Parentpeak, 164, of D-9-2-phenylpyridine was observed in MS spectrum, and alsoD-24-Ir(ppy)3 showed 678.7 as the parent peak.

Example 9 Deuterated Alq3: Green Luminescent Compound Preparation

[0071]

[0072] By using the deuterated quinoline 29, green luminescent metalcomplex 35, deuterated tris-(8-hydroxyquinoline) aluminum, can beprepared according to the above scheme with the similar procedures andapplication mechanism as described in: [Kuznetsoua, “Complex compoundsof metals with some nitrogen containing ligands”, Zhurnal obshcheykhimii, vol. XLVI (CVIII), No. 3, Mar. 1976, pp. 670-675; Hamada et al.,“Organic Electroluminescent Devices with 8-HydroxyquinolineDerivative-Metal Complexes as an Emitter,” Japanese Journal of AppliedPhysics, vol. 32, Part 2, No. 4A, Apr. 1, 1993, pp. L514-L515; Tang etal., “Organic electroluminescent diodes,” Applied Physics Letters, vol.51, No. 12, Sep. 21, 1987, pp. 913-915.]

Example 10 Electroluminescence of fac-tris(2-phenylpyridine)iridiumIr(ppy)3 (for comparison)

[0073] A device of ITO/NPD 40 nm/CBP+11% Ir(ppy)₃ 20 nm/BCP 10 nm/Alq340 nm/LiF 0.75 nm/Al, where NPD denotes toN,N′-bis(naphthyl)-N,N′-diphenylbenzidine, CBP denotes to carbazolebiphenyl, was fabricated following a similar procedure as described in:Appl. Phys. Lett., 75, 4 (1999). Each layer was formed and controlled byvacuum thermal evaporation. The NPD was used as a hole transportinglayer; the CBP was used as the host with the phosphorescent dopant,Ir(ppy)₃, as the emissive layer; BCP was used as the exciton blockinglayer; Alq3 as electron transporting layer; LiF was used as cathodemodification layer; Al was used as the cathode metal. Bright greenluminescence (electrophosphorescence) was observed at a voltage of 5 V.The electroluminescence spectrum was shown in FIG. 6.

Example 11 Electroluminescence of fac-tris(2-phenylpyridine)iridium-d8Ir(ppy)₃-d8

[0074] A device of ITO/NPD/CBP+11% Ir(Ppy)₃-d8 20 nm/BCP 10 nm/Alq3 40nm/LiF 0.75 nm/Al, was fabricated following a similar procedure asdescribed in Example 10. Bright green luminescence(electrophosphorescence) was observed at a voltage of 5 V. Theelectroluminescence spectrum was shown in FIG. 7.

[0075]FIG. 8 shows the relationship of quantum efficiency (%, photonsper electron) vs. current density (mA/cm²) for the device in Example 10(square symbols) with the device of Example 11 using deuteriumIr(ppy)3-d8 (circle symbols). From FIG. 8, the device of Example 11 hashigher quantum efficiency than the device of Example 10.

[0076]FIG. 9 shows the relationship of luminance efficiency (lm/W) vs.current density (mA/cm²) for the device in Example 10 (square symbols)with the device of Example 11 using deuterium Ir(ppy)3-d8 (circlesymbols). From FIG. 9, the device of Example 11 has higher luminanceefficiency than the device of Example 10.

[0077] It will be appreciated that the present invention provides neworganic semiconductor materials that exhibit high luminescence,excellent stability, and good lifetime. This is achieved by chemicallymodifying known and novel optoelectronic materials by replacing protonswith deuterium atoms on the conjugated chromophores. New luminescentorganic materials are designed and synthesized containing deuteriumatoms for their application in optoelectronic devices, includinglight-emitting devices. Such OLEDs prepared with deuterated organicsemiconductor materials have brighter luminance and better thermalstability compared to non-deuterated organic semiconductor materials.

[0078] The present invention may be embodied in other specific formswithout departing from its essential characteristics. The describedembodiments are to be considered in all respects only as illustrativeand not restrictive. The scope of the invention is, therefore, indicatedby the appended claims rather than by the foregoing description.

1. An organic semiconductor comprising a conjugated chromophore selectedfrom a linear conjugated organic compound or a polymer, a cyclic ring, afused cyclic ring, a heterocyclic ring, a fused heterocyclic ring, achelate or oraganometalic material having the formula CAMB, where Cdenotes a conjugated chromophore, M denotes a metal selected from, Li,Na, K, Be, Mg, Ca, Ti, Cr, Mo, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt,Cu, Zn, Cd, B, Al, Ga, In, Si, N, P, and A and B denote a number from 1to 10, respectively, and combinations thereof, said chromophore havingwith at least 5 conjugated bonds wherein protons linked to theconjugated bonds are partially or fully deuterated.
 2. An organicsemiconductor according to claim 1, wherein the conjugated chromophoreis partially deuterated, and wherein un-deuterated sites are chemicallybound to a moiety selected from hydrogen atoms, halogen atoms, alkyl,alkoxyl, thiol, silyl, aromatic rings, or heteroaromatic rings.
 3. Anorganic semiconductor according to claim 1, wherein the organicsemiconductor is luminescent.
 4. An organic semiconductor according toclaim 1, wherein the organic semiconductor possesses charge injection,hole blocking, or exciton blocking properties.
 5. An organicsemiconductor according to claim 1, wherein the organic semiconductorpromotes energy transfer.
 6. An organic semiconductor according to claim1, wherein the organic semiconductor produces greater than 25% singletexcitons for light emission.
 7. An organic semiconductor comprising aconjugated chromophore with a linear conjugated organic compound or apolymer with at least 5 conjugated bonds, wherein protons linked to theconjugated bonds are partially or fully deuterated.
 8. An organicsemiconductor according to claim 7, wherein the conjugated chromophoreis partially deuterated, and wherein un-deuterated sites are chemicallybound to a moiety selected from hydrogen atoms, halogen atoms, alkyl,alkoxyl, thiol, silyl, aromatic rings, or heteroaromatic rings.
 9. Anorganic semiconductor according to claim 7, wherein the organicsemiconductor is luminescent.
 10. An organic semiconductor according toclaim 7, wherein the organic semiconductor possesses charge injection,hole blocking, or exciton blocking properties.
 11. An organicsemiconductor according to claim 7, wherein the organic semiconductorpromotes energy transfer.
 12. An organic semiconductor according toclaim 7, wherein the organic semiconductor produces greater than 25%singlet excitons for light emission.
 13. An organic semiconductorcomprising a conjugated chromophore with a cyclic ring, a fused cyclicring, or a combination thereof, in the form of a conjugated organiccompound or a polymer with at least 5 conjugated bonds, wherein protonslinked to the conjugated bonds are partially or fully deuterated.
 14. Anorganic semiconductor according to claim 13, wherein the conjugatedchromophore is partially deuterated, and wherein un-deuterated sites arechemically bound to a moiety selected from hydrogen atoms, halogenatoms, alkyl, alkoxyl, thiol, silyl, aromatic rings, or heteroaromaticrings.
 15. An organic semiconductor according to claim 13, wherein theorganic semiconductor is luminescent.
 16. An organic semiconductoraccording to claim 13, wherein the organic semiconductor possessescharge injection, hole blocking, or exciton blocking properties.
 17. Anorganic semiconductor according to claim 13, wherein the organicsemiconductor promotes energy transfer.
 18. An organic semiconductoraccording to claim 13, wherein the organic semiconductor producesgreater than 25% singlet excitons for light emission.
 19. An organicsemiconductor of the formula CAMB, where C denotes a conjugatedchromophore, wherein protons linked to the conjugated bonds arepartially or fully deuterated; M denotes a metal selected from, Li, Na,K, Be, Mg, Ca, Ti, Cr, Mo, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu,Zn, Cd, B, Al, Ga, In, Si, N, and P; A and B denote a number from 1 to10, respectively.
 20. An organic semiconductor according to claim 19,wherein A and B denote a number from 1 to 4, respectively.
 21. Anorganic semiconductor according to claim 19, wherein the conjugatedchromophore is partially deuterated, and wherein un-deuterated sites arechemically bound to a moiety selected from hydrogen atoms, halogenatoms, alkyl, alkoxyl, thiol, silyl, aromatic rings, or heteroaromaticrings.
 22. An organic semiconductor according to claim 19, wherein theorganic semiconductor is luminescent.
 23. An organic semiconductoraccording to claim 19, wherein the organic semiconductor possessescharge injection, hole blocking, or exciton blocking properties.
 24. Anorganic semiconductor according to claim 19, wherein the organicsemiconductor promotes energy transfer.
 25. An organic semiconductoraccording to claim 19, wherein the organic semiconductor producesgreater than 25% singlet excitons for light emission.
 26. An organicsemiconductor according to claim 1, fabricated as an organic luminescentdevice.
 27. An organic semiconductor according to claim 7, fabricated asan organic luminescent device.
 28. An organic semiconductor according toclaim 13, fabricated as an organic luminescent device.
 29. An organicsemiconductor according to claim 19, fabricated as an organicluminescent device.
 30. An organic luminescent device comprising: afirst electrode surface; a first thin film of conjugated luminescentpolymer comprising an organic semiconductor according to claim 1,wherein the luminescent polymer is electrically coupled to the firstelectrode surface; and a second electrode, electrically coupled to theconjugated luminescent polymer.